Waste and Biomass Valorization (2021) 12:3125–3136

https://doi.org/10.1007/s12649-020-01128-9

ORIGINAL PAPER

Closed‑Loop Recycling of Copper from Waste Printed Circuit Boards

Using Bioleaching and Electrowinning Processes
Mahsa Baniasadi1,2,5 · John E. Graves1,3 · Daniel A. Ray1,2,5 · Angélique Lindamulage De Silva4 · Derek Renshaw1,2 ·
Sebastien Farnaud1,2 

Received: 28 February 2020 / Accepted: 13 June 2020 / Published online: 29 June 2020
© The Author(s) 2020

Abstract
In the present study, a model of closed-loop recycling of copper from PCBs is demonstrated, which involves the sequential
application of bioleaching and electrowinning to selectively extract copper. This approach is proposed as part of the solution
to resolve the challenging ever-increasing accumulation of electronic waste, e-waste, in the environment. This work is target-
ing copper, the most abundant metal in e-waste that represents up to 20% by weight of printed circuit boards (PCBs). In the
first stage, bioleaching was tested for different pulp densities (0.25–1.00% w/v) and successfully used to extract multiple met-
als from PCBs using the acidophilic bacterium, Acidithiobacillus ferrooxidans. In the second stage, the method focused on the
recovery of copper from the bioleachate by electrowinning. Metallic copper foils were formed, and the results demonstrated
that 75.8% of copper available in PCBs had been recovered as a high quality copper foil, with 99 + % purity, as determined
by energy dispersive X-ray analysis and Inductively-Coupled Plasma Optical Emission Spectrometry. This model of cop-
per extraction, combining bioleaching and electrowinning, demonstrates a closed-loop method of recycling that illustrates
the application of bioleaching in the circular economy. The copper foils have the potential to be reused, to form new, high
value copper clad laminate for the production of complex printed circuit boards for the electronics manufacturing industry.
Graphic Abstract

Keywords  Bioleaching · Copper recovery · Electrowinning · Printed circuit boards · Recycling · WEEE

* Sebastien Farnaud
sebastien.farnaud@coventry.ac.uk
Extended author information available on the last page of the article

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Statement of Novelty
The use and value of copper are high and so there are both
environmental and economic drivers for recovering cop-
per efficiently. Redundant Printed Circuit Boards (PCBs)
constitute a rich source of copper. The focus of this work
is the demonstration of ‘closed-loop’ recycling of copper
from PCBs via bioleaching and electrowinning processes.
Typically, ion exchang or solvent extraction techniques are
required to concentrate and purify the dissolved copper
before electrowinning. These processes add expense and
in the latter case use toxic, low flash point solvents. This
work confirms the recovery of a pure copper product, in
good yield, by electrowinning directly from bioleachate.
The new process is shorter, more cost-efficient and an
environmentally friendly means of recycling the valuable
metal.
Introduction
Every year, 72% of copper extracted from natural
resources, with high cost and energy consumption, is used
for the production of electrical and electronic equipment
[1]. In addition to the depletion of natural resources, metal
recovery from primary resources has a high carbon foot-
print, with an estimated 127 Mt C ­ O2eq of greenhouse gas
globally [2]. Due to consumer demand and rapid techno-
logical innovation, electrical and electronic equipment has
a short life span. Within a few years, discarded equipment
including the bulk of the metal content is predominantly
sent to landfill, which demonstrates an environmentally
unsustainable approach that is commonly practiced in the
IT industry [3]. To address these issues, urban mining is
being developed to promote a circular economy and the
reuse of metals in electrical and electronic equipment.
This new trend has transformed waste electrical and elec-
tronic equipment (WEEE) into a secondary source of met-
als [4]. Methods traditionally used for metal extraction
from ores in the mining industry, including pyrometal-
lurgy, hydrometallurgy but also bioleaching, can be used
to extract metals from secondary resources.
Several commercialized plants worldwide are avail-
able for recycling of e-waste by either hydrometallurgy or
pyrometallurgy. For instance, Dowa Eco-System published
the use of advanced metallurgical methods to recycle up
to 22 metal elements [5]. Similarly, Boliden Rönnskär,
claims to produce 201 kt copper, 33 kt zinc clinker, 26 kt
lead, 384 tons silver and 12 tons gold in 2019 from recy-
cling of e-waste [6]. In addition to scrap products from
the electrical and electronic engineering industries, metal
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Waste and Biomass Valorization (2021) 12:3125–3136
recovery plants are also essential to process other solid
wastes including emission control catalyst, rechargeable
batteries, bottom ash/fly ash and heavy metal-containing
sludge [7]. Despite technology readiness, pyrometal-
lurgy and hydrometallurgy, which are still widely used
in industry, remain very challenging for the environment.
Pyrometallurgy is highly energy-intensive as it requires
smelting at 300–900 °C and, when applied to WEEE, it
may cause the emission of toxic gases, such as furan and
dioxin due to the presence of brominated flame retardants
[8, 9]. Similarly, by using toxic chemical solutions, which
include sulphuric acid, nitric acid, hydrochloric acid and
hydrogen peroxides, hydrometallurgy techniques expose
natural water resources to the risk of acidification and
pollution, for which sophisticated wastewater treatment
techniques are required [10]. A comparative study between
bioleaching and hydrometallurgy processes, regarding
their environmental impact for copper and zinc recovery
from PCBs [9] confirmed that of all recycling methods
applied to metal treatment, bioleaching, which uses bac-
teria to recover metals from a solid matrix, remains the
most sustainable method for metal recovery from WEEE;
bioleaching has 0.4 kg ­CO 2eq whereas hydrometallurgy
had 0.7 kg ­CO2eq carbon footprint [8]. In addition to its
environmental benefits, bioleaching requires less invest-
ment than conventional metal recovery methods [8]. It
should also be noted that the most widely used bacteria in
bioleaching are acidophilic bacteria that have been isolated
from the natural environment [11].
An important component in almost all electrical and
electronic equipment is the printed circuit board (PCB). In
this study, PCBs originating from IT networking and tel-
ecommunication equipment, which to our knowledge have
not been investigated as a source of electronic waste for
bioleaching and electrowinning, are investigated for cop-
per recycling. Networking and telecommunication facilities
contain switchboards that are rich sources of critical met-
als, which provide environmental and economic incentives
for recovery. In particular, boards from outdated technology
contain higher levels of precious metals. PCBs are generally
manufactured from polymers, metals and ceramics, with a
very heterogeneous metallic fraction containing over 20 dif-
ferent elements including noble, base and rare earth metals
[12]. Whereas the polymer content of PCBs can be used for
the production of liquid and gas fuel through thermochemi-
cal methods such as gasification and pyrolysis [13, 14], the
most abundant metal in all types of PCBs is copper, which
is commonly used due to its high conductivity and relatively
low cost [1].
Bioleaching converts metals attached and buried in the
laminar PCB from their elemental state into solubilised
metallic ions [8]. Acidithiobacillus ferrooxidans, which is
the most commonly used bacterial species for bioleaching,
Waste and Biomass Valorization (2021) 12:3125–3136 3127
has been proven successful for metal recovery from several
e-waste sources, including lithium ion batteries [15, 16],
Ni–Cd batteries [17], computer PCBs [18], mobile phone
PCBs [19] and light emitting diode (LED) lamps [20]. The
effects of different pulp densities of e-waste (LED lamps) on
metabolic activity and adaptation of A. ferrooxidans, have
been described elsewhere, and concluded that the maximum
pulp density of LED lamp that A. ferrooxidans can tolerate
is 1.5% w/v [21].
To recover the metal in its final pure elemental state for
reuse in a new product, several methods have been proposed
including cementation, sulphide precipitation, ion exchange
and electrowinning [22–24]. Electrowinning process is the
method expected to provide the highest purity of final prod-
uct in a form of copper foil [25]. However, the heterogeneous
metal content of PCBs is challenging for electrowinning, as
the bioleachate mixture resulting from the leached waste
contains several other base metals and components in addi-
tion to copper. The novelty of this work is combining both
technologies, the electrowinning process with bioleaching.
Selective electrowinning of copper that can deliver a valu-
able, high purity product from such a complex mixture of
metals and metabolites, is a challenge, particularly with the
significant amount of iron that is required as the electron
donor in the bioleaching process for acidophiles [26].
Electrowinning was combined with leaching of elec-
tronic waste in other research works [27–29], but although
bioleaching has been investigated as a sustainable method
for metal solubilisation from PCBs, to our knowledge,
applying electrowinning directly to the bioleachate has not
been considered before. Recently, a cementation method for
metal recovery from e-waste was tested and copper with 93%
purity was obtained, but the product was in the form of cop-
per precipitates [25]. For metal recovery from the solution
obtained from bioleaching of PCBs, solvent extraction has
been applied [30], a process that is followed by electrowin-
ning. The purity of the recovered copper was reported to be
99.83% pure. In the present work, electrowinning of cop-
per directly from bioleachate is reported for the first time.
This process avoids the need for solvent extraction, reduces
operational costs and eliminates the use of toxic, low flash
point solvents [31].
Materials and Method
PCB Characterisation
The PCBs used in this work were obtained from switch
boards of IT networking and telecommunication equipment,
which were manufactured by Alcatel in 2001. The PCBs
were shredded using an industrial shredder. Although the
optimal particle size for bioleaching has been reported to
be 100 microns [32], such small size particles have been
avoided in this work, in order to adopt the most sustainable
process that would reduce energy consumption, dust forma-
tion and loss of valuable metals.
Metal content of the ashed PCB sample was determined
as follows: samples were first ashed at 550 °C for 12 h in
a furnace (Lenton, ECF) to remove volatile fractions; then
digested in aqua regia at 70 °C on a hot plate for 24 h. Fol-
lowing filtration, the resulting solution was analysed by
Inductively-Coupled Plasma Optical Emission Spectrom-
etry (ICP-OES) using a Perkin Elmer Optima 8300 and
calibrated using standard solutions obtained from Merck
(TraceCERT®). This calibration was carried out using
diluted standard solutions using a five point standard range
(10–100 mg/l). The correlation coefficient for copper was
0.9997.
Bioleaching Method
The acidophilic bacterium used in this study was A. ferroox-
idans, from the Acidophile Laboratory Bangor University,
Wales, UK. A. ferrooxidans is chemolithoautotroph sulphur
and iron-oxidising bacterium, which is able to convert fer-
rous iron to ferric, so that in turn ferric ions oxidise the
base metals available in PCBs and solubilise them in their
ionic form. Bacteria were grown in 9 k medium contain-
ing: ­(NH4)2SO4 3.0 (g/l), KCl 0.1 (g/l), K ­ 2HPO4 0.5 (g/l),
­MgSO4·7H2O 0.5 (g/l), Ca(NO3)2 0.01(g/l), F ­ eSO4·7H2O
44.2 (g/l), in distilled water, with pH adjusted to 2.0, using
sulphuric acid (1.0  M). Each 250  ml Erlenmeyer flask
contained 100 ml of medium. The bacteria were grown in
a shaker-incubator at 30 °C and agitated at 50 rpm. The
adopted method was a two-step bioleaching process, where
the electronic waste was added after the growth phase of
the bacteria. The growth curve of A. ferrooxidans has been
characterised elsewhere [21, 33] by cell counting. In the first
2 to 4 days following inoculation, the bacterial population
increased exponentially during the log phase; in two-step
bioleaching, the addition of e-waste is carried out follow-
ing the log phase at the start of stationary phase, which is
considered as full bacterial growth. In the current study,
before the addition of e-waste, the concentration of ferric
ions increased from 0 at time of inoculation, to a maximum
of 7.8 g/l after 2 days. Similarly, after 2 days of growth, the
oxidation reduction potential (ORP) had climbed from an
initial 310 mV at inoculation to 510 mV. Both increased
parameters indicated full bacterial growth.
Once full growth had been reached, sterilised shredded
PCBs were added to the flasks at a pulp density within the
range of 0.25–1.00% w/v. The rotation speed was increased
to 160 rpm for the bioleaching process. Daily sampling was
performed to monitor the change in pH of the solution, the
ORP of the medium, the concentration of ferric ions and
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3128 Waste and Biomass Valorization (2021) 12:3125–3136

metal content by ICP-OES analysis. A Thermo Scientific
pH meter was used to monitor pH and a Thermo Scientific
Sure-Flow Combi Redox/ORP electrode filled with Ag/AgCl
solution was used for the Redox measurements. It was cali-
brated daily using Thermo Scientific ORP standard 900,011.
Ferric ion concentration was determined by spectrophotom-
etry using the 5-sulfosalicylic acid method. This method
relies on the reaction of 5-sulfosalicylic acid with ferric ions
available in the medium, which translates into a violet color,
intensity of which is measured with a spectrophotometer at
500 nm. The color intensity can be translated into a concen-
tration, using a calibration curve obtained from dissolution
of ­Fe2(SO4)3 at defined concentrations in distilled water [34].
The nature and concentration of metals in the solution were
determined at the end of bioleaching process, after filtration
with Whatman filter paper Grade 541, using the ICP-OES
method mentioned in Sect. 2.1. These values were further
used to determine the metal recovery efficiency.
Electrowinning
and the percentage of copper recovery of the electrowin-
ning process was calculated. As the pH of the bioleachate
was 2.0, the pH of mimic solutions was also adjusted to
pH 2.0 using 1 M sulphuric acid.
Product Characterisation
The obtained foils were analysed using a Carl Zeiss, 1530
VP field emission gun scanning electron microscope (FEG-
SEM) and energy dispersive X-ray (EDX) analysis for mor-
phology and purity respectively. The accelerating voltage
used for secondary electron imaging and EDX was 20 kV.
The surface morphology was examined on the final prod-
uct after electrodeposition and foil removal. Energy disper-
sive X-ray (EDX) analysis was carried out using an Oxford
Instruments X-Max 80 ­mm2 EDX detector. The thickness
of the copper was also measured by viewing prepared foils
on the SEM. The purity of the foil was also confirmed using
ICP-OES analysis, after digestion of foil with aqua regia.

To determine the optimum conditions for electrowinning,

mimic solutions with metal concentrations similar to the
bioleachate were used. The concentration of all metals in Results and Discussion
the bioleachate were determined by ICP-OES; the mimic
solution in the first step, was prepared using sulphate salts PCB Content
of each metal in equivalent amount. In the next set, a 9 k
medium solution was prepared that contained all the com- The metal content, which was determined by ICP-OES,
ponents mentioned in Sect. 2.2. However, the amount of was calculated to contain 36.11 wt% base metals, 0.01
iron was defined according to the ICP-OES results. The wt% rare earth metals and 0.02 wt% precious metals. The
electrowinning tests were performed in a cell containing detailed metal concentration of the PCB (Table 1) showed
an anode and a cathode. The cathode was a 316 stain- that the most abundant metal was copper, which represents
less steel sheet (length: 9 cm, width: 2 cm and 0.1 cm 29.04 wt% of the e-waste. This value is in the mid-range of
thickness) and the anode was an insoluble titanium mesh the copper content as reported by other researchers [12].
coated in a mixed metal oxide ­(IrO2-Ta2O5). The leachate In addition to base metals, noble metals were also identi-
was stirred at 500 rpm using a magnet stirrer to facili- fied. For example, gold, which is used widely in PCBs
tate the transport of metal ions to the cathode surface. A for its stability (excellent corrosion resistance, good wear
fairly high stirring rate was chosen to avoid mass transport resistance when alloyed with other metals) and high con-
limitations from convection processes. The reverse side ductivity, was found to be present in significant quantities.
of the stainless steel plate was covered with plating tape Furthermore, other metals such as gallium, present in gal-
(RS components) to prevent copper deposition. The area lium nitride (GaN) transistors as semi-conductive materi-
of the cathode immersed in solution was calculated as 8 als [35], as well as the rare earth element neodymium,
­c m 2. The plating time for actual bioleachate was set at found in magnetic actuators, were identified [36].
3 h, a value obtained as optimal time in this work, after
investigating the effect of electrowinning time on plating
efficiency and quality of the product. The current den- Table 1  PCB metal content (mg/g PCB)
sity was set at 10 mA/cm2. Assuming 100% efficiency,
Cu Cr Ga Fe Pb Mn
the mass of copper deposited under these conditions is
290.37 0.02 0.05 8.23 17.84 2.27
theoretically 0.28 g after 3 h. It is expected that this mass
Mg Ni Al Ag Zn
of copper should form a 40 µm thick foil for this electrode
1.20 3.52 33.89 0.08 3.67
area. The actual mass of the plated copper was calculated
Au Pd Pt Nd
by measuring the weight of the cathode before and after
0.17 0.05 0.01 0.11
electrowinning. From these values the current efficiency

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Waste and Biomass Valorization (2021) 12:3125–3136 3129
Bioleaching Results
Heavy metals and organic materials, such as epoxy polymer
and brominated flame retardants available in PCBs, have some
toxic effects for the growth and activity of bacteria [37]. The
toxicity of organic and inorganic anions, except sulphate, is
more challenging for acidophilic bacteria than transition metal
cations [38]. This can present a limitation to the amount of
PCBs that can be processed in each batch. The effects of pulp
density on growth and activity of bacteria is shown in Fig. 1.
When ferrous ions act as electron donor for bacteria, elec-
trons travel across the bacterial membrane, against the redox
potential gradient in an uphill pathway. This process requires
energy, which is obtained from the influx of protons into the
bacteria via the proton gradient that is created by the acidic
pH of the medium. These protons are also suggested to be
involved in the reduction of oxygen to water, again relying on
the proton gradient caused by the difference in internal and
external pH [39].
In the presence of A. ferrooxidans, two reactions are taking
place in the medium, where Eq. 1 is the biological reaction and
Eq. 2 is the chemical hydrolysis of ferric ions [17]:
1 The same trends were reported for the bioleaching of
2Fe2+ + O2 + 2H+ → 2Fe3+ + H2 O (1)
2
Fe3+ + nH2 O → Fe(OH)(3−n)+
n
+ nH+ (2)
Fig. 1  a pH, b ferric ion concentration versus bioleaching time as an
indication of bacterial growth and activity for different pulp densities
Following the addition of metal-containing e-waste ( M0 )
(Eq. 3), an initial pH increase was observed, which is pro-
posed to be the result of: (1) the alkali reaction due to the
cleavage of amine curing agents from in epoxy resin [37],
and (2) a decreased proton production by Eq. 2 due to the
consumption of ferric ions as described in the redoxolysis
reactions (Eq. 3).
M0 + 2Fe3+ → M2+ + 2Fe2+ (3)
During the bioleaching process, epoxy goes through
depolymerization through proton consumption. The epoxy
content of e-waste is depolymerized after cleavage of bis-
phenol monomers, a very weak organic acid, and amine cur-
ing reagents [37]. As shown in Fig. 1a, the higher the pulp
density, the sharper the pH increase, as more PCB is released
into the medium. Reciprocally, at the later stage, a decrease
in pH can be observed: as the remaining metal content in
the solid waste decreases, less ferric ions are consumed, as
described in Eq. 3 and more ferric ions remain available for
Eq. 2, so the proton production increases as by reaction men-
tioned in Eq. 2. In addition, the rate of Eq. 1 also decreases
as the bacteria reaches its death phase.
button-cell batteries in another research work [40]. Finally,
the pH stabilises and becomes constant after three days of
bioleaching. The role of the bacteria can be seen as the con-
tinuous generation of metabolites that can act as leaching
agents [41]. Lower ferric ion concentration in the medium,
with higher amount of PCBs, is due to the lower rate of
regeneration cycle (biological conversion of ferrous to fer-
ric ions with Eq. 1) during bioleaching, due to the toxicity
of PCBs and their inhibitory effect and more consumption
of ferric ions in Eq. 3 as more metals are available in the
medium. The decrease in the amount of ferric ions (Fig. 1b)
was due to the formation of jarosite at higher concentration
of ferric ion and higher pH. This reaction took place at a
pH greater than 2, and by reaction of ferric hydroxides with
monovalent cations including K ­ H4+, available in the
­ + and N
9 k medium [42]. Since A. ferrooxidans is both an iron and
sulphur oxidizing bacteria, it can be expected that a lower
jarosite formation would lead to a higher bioleaching rate,
and would facilitate the consumption of ferrous sulphate in
the process as will be discussed later in Sect. 3.5.
Analysis of variance (ANOVA) with α = 0.05 of the
obtained results (Table 2) Indicates a significant effect of
pulp density on both parameters (pH and ferric ion concen-
tration) indicated by very low F-values. Figure 2 illustrates
change of ORP with time. No significant effect of pulp den-
sity on ORP was observed. In a two-step bioleaching proce-
dure, electronic waste is added when the ORP is high as it is
the beginning of stationary phase when the maximal amount
of ferric ions is available in the solution. It was suggested
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3130 Waste and Biomass Valorization (2021) 12:3125–3136

Table 2  Analysis of variance Source of Variation SS df MS F P-value F crit

(ANOVA) for pH, and ferric
concentration ANOVA for pH
 Pulp density 0.568 3 0.189 40.478 0.000 2.748
 Time 1.398 7 0.200 42.685 0.000 2.156
 Interaction 0.059 21 0.003 0.600 0.903 1.723
 Within 0.299 64 0.005
 Total 2.325 95
ANOVA for ferric con-
centration
 Pulp density 68.787 3 22.929 96.121 0.000 2.748
 Time 77.424 7 11.061 46.367 0.000 2.156
 Interaction 6.961 21 0.331 1.390 0.158 1.723
 Within 15.267 64 0.239
 Total 168.439 95

leaches other base metals from the PCBs, by redoxolysis

Fig. 2  ORP vs. bioleaching time (pulp density 1% w/v)
and acidolysis mechanisms. Redoxolysis refers to electron
exchange reaction between elemental metals and the fer-
ric-ferrous redox couple. Only metals that have a standard
potential with higher negative value than that of the ferric-
ferrous redox couple in a standard oxidation-potential table
can go through this reaction. As an example, aluminium can
be dissolved through electron exchange with ferric ions.
However, aluminium is typically coated with a thin layer
of protective oxide. The oxide can be dissolved by acidoly-
sis (proton attack: Al2 O3 + 6H+ → 2Al3+ + 3H2 O [43]), so
that the exposed aluminium can undergo electron exchange
with ferric ions (redoxolysis). As such, the bioleaching reac-
tion continued for 8 days, when 100% copper recovery with
bioleaching was achieved. In addition to copper, the biolea-
chate contains other metals including iron and magnesium,
which have been either fed into the medium or bioleached
from PCBs (Table 3). This resulting mixture in the biolea-
chate entails a challenging selective copper recovery from
the bioleachate, which could be heterogeneous due to pres-
ence of several other base metals and components that might
interfere with plating of copper.

Electrowinning Results

The bioleachate obtained from the highest pulp density, the

Fig. 3  Metal recoveries for 1.0% w/v pulp density
that the initial ORP increase observed after e-waste addition
could be due to the destruction of metal oxides available in
e-waste, which increase the amount of dissolved oxygen in
the medium [40].
As illustrated in Fig. 3, the metal recovery by bioleaching
for the flasks with 1.00% w/v PCBs, in addition to copper,
composition of which was determined by ICP analysis and is
described in Table 3, was used for electrowinning. Standard
reduction potentials are also given for the metals present in
the bioleachate. For cupric ions the reduction half reaction
is:
Cu2+ + 2e− → Cu0 (4)
The standard reduction potential, E°, is + 0.34 V and
the Gibbs free energy, ΔG, − 66 kJ. Nickel, iron, zinc and

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Waste and Biomass Valorization (2021) 12:3125–3136 3131

Table 3  Bioleachate metal composition and standard potentials of metals

Ability of metal ions to acquire electrons and undergo reduction increases

Metal Na Mg Al Mn Zn Fe Ni Cu

Concentration (mg/l) 17 56 180 6 19 400 17 2903

Standard potential (V)  − 2.71  − 2.37  − 1.6  − 1.19  − 0.76  − 0.45  − 0.26  + 0.34

manganese ions may also be reduced to their base metal,

but their standard reduction potentials have negative values,
see Table 3, and all half reactions therefore have a positive
ΔG. The reduction of these metals is less likely, and so the
cupric ions ability to readily accept electrons and undergo
reduction make it the more likely species to be reduced to its
base metal. For sodium, magnesium, and aluminum, there
is no possibility of metallic ion reduction at the cathode,
the decomposition of water into hydrogen will be the more
favorable reaction [44].
The reaction at the mixed metal oxide anode [45] is the
oxidation of water into oxygen (Eq. 5), although the possibil-
ity of oxidizing ferrous back to ferric cannot be excluded,
in which case any ferric generated can be recycled to the
bioleaching unit to accelerate the metal dissolution process.

2H2 O → O2 + 4H+ + 4e− (5)

Electrowinning was performed first on a mimic solution

containing metallic ions as expressed in Table 3 for 5 h. The
cell voltage, on average, was equal to 2 V during the elec-
trowinning process. Every hour the cathode was taken out
and weighed to calculate the amount of copper deposited
on the cathode. The theoretical mass of copper plated was
calculated from the charge passed according to Faraday’s
laws summarized as:
itM
w= (6) Fig. 4  a Mass of copper collected at cathode versus time b current
zF
efficiency versus time
in which w is the mass of copper plated, i is the set current
(A), t is electrowinning time (s), M is the metal molecular
weight, z is the number of electrons (2 in this case) and F is calculated theoretical rate, 0.09 g/h. During the last hour
the Faraday constant (96,485 C ­mol−1). of the experiment, the observed rate dropped to 0.01 g/h.
The mass gain of the cathode versus electrowinning A plot of the current efficiency versus time (Fig. 4b) also
time for the mimic solution containing all metals, is shown confirms this observation. The current efficiency drops
in Fig. 4a. It can be seen that as the electrowinning time from 91 to 59% after 5 h. It can be explained by the over-
increases the mass of copper deposited on the cathode all decrease in cupric ion concentration in the leachate.
falls below the theoretical value expected. After the first At low concentrations, the mass transport of ions to the
hour of the test, the actual rate of deposition is close to the electrode surface becomes the limiting factor, and other
electrochemical reactions, other than copper deposition,

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3132 Waste and Biomass Valorization (2021) 12:3125–3136

Analysis of the Copper Product

Following the electrowinning tests, the copper foil produced

Fig. 5  Foil appearance versus time from mimic solution with all met-
als (according to Table 2) after a 1 h, b 2 h, c 3 h, d 4 h e 5 h
can occur [46]. Figure 5 illustrates the accumulation of the
copper deposit over time. As the electrowinning process
progresses, it can be seen that the deposit darkens and
becomes rougher. This is also clear evidence that another
electrochemical reaction such as hydrogen evolution is
taking place at the copper cathode in the latter stages of
the experiment [47].
Based on the above results, a time of 3 h was selected
as the total plating time for future electrowinning tests
from (1) a mimic solution containing all metals present in
9 k medium, (2) the bioleachate obtained from 1.00% w/v
PCBs. Each test was performed in 3 replicates. Success-
ful copper plating was obtained from the two solutions
at good recovery (75% +) and current efficiency values
(80% +), see Table 4, at a current density of 10 mA/cm2.
To maintain these high values, the electrowinning process
should run as a ‘feed and bleed’ system in order to main-
tain the copper concentration ≥ 2 g/l. The ‘bleed’ from the
electroplating unit, depleted of cupric ions, can be returned
back to the bioleaching unit where the ferrous ions can be
converted back to ferric ions for continued dissolution of
base metals from the PCB pulp. The accumulation of other
metal ions in the leachate can continue until their concen-
tration is suitable for processing by electrowinning or an
ion-exchange recovery unit.
was manually peeled away from the stainless steel cathode /
substrate. The morphology and purity of the copper deposit
were analysed using the SEM–EDX system and ICP-OES
as described in Sect. 2.4. Figure 6a shows a micrograph of
the copper foil obtained from the mimic 9 K medium / metal
ion solution. A nodular, compact deposit was observed at the
plating current density of 10 mA/cm2. Analysis of the foil by
EDX showed a high purity copper deposit (99.6%), as seen
in Fig. 6b. The carbon present in the spectrum is an artificial
peak from hydrocarbon contamination, which often induces
a background carbon signal, and can be ignored. A small
amount of oxygen is also present that can be attributed to
the reaction of the copper surface with atmospheric oxygen.
The reduction of other aqueous metal ions, see Table 3, are
clearly not favorable at the electrode surface. Once plated
with copper, the stainless steel substrate effectively becomes
a copper electrode. Copper is a good electrocatalyst for
hydrogen evolution, and as such, the reduction of protons to
hydrogen gas is the favoured reaction when the mass trans-
port of cupric ions is the limiting factor. Furthermore, the
presence of the 9 K medium does not interfere with copper
deposition and foil formation on the stainless steel cathode
is still possible.
Figure 7a shows a photograph of the foil as the result of
electrowinning from a bioleachate at 1.00% w/v pulp density.

Table 4  Electrowinning recovery and current efficiency of mimic

solution and bioleachate

Solution Recovery (%) Efficiency (%)

Mimic solution containing 85.3 87.0

all metals in 9 k medium
Bioleachate obtained from 75.8 80.6
1.00% w/v PCBs Fig. 6  Analysis of copper foil obtained from mimic solution contain-
ing metals in 9 K medium a SEM b EDX

13
Waste and Biomass Valorization (2021) 12:3125–3136 3133
Fig. 7  a Final product from bioleachate as a foil b foil morphology
with SEM c EDX analysis of foil
The SEM micrograph (Fig. 7b) of the copper foil exempli-
fies a typical copper electroplated surface [48, 49], and a
purity of deposit of 98.5% was measured by EDX (Fig. 7c).
Again the carbon peak from contamination can be ignored
and the EDX result was confirmed by ICP-OES analysis,
which determined 99.55 wt% copper, 0.25 wt% sulphur and
0.2 wt% potassium. Previously, very high purity copper
(99.83%) was obtained by combining solvent extraction and
electrowinning processes [31]. Obtaining very high purity
copper without using solvent extraction, as achieved in this
study, has several environmental and economic benefits.
Another study, that extracted copper with cementation with
zinc, after separation of iron with precipitation, obtained
copper precipitate with 95% purity, but not in the form of
foil [9]. Moreover, an electrowinning process is scalable and
foil can be recovered in a continuous process using a rotating
drum electrode [50].
The high purity (+ 99%) copper product obtained here
from bioleachate using a single electrowinning process dem-
onstrates that there is no need for solvent extraction. The
high purity foil indicates that the electrowinning has been
performed selectively. This selective extraction of copper,
without solvent extraction, reduces the operational costs and
eliminates the requirement for a toxic, low flash point sol-
vent. This novel approach of copper separation from WEEE
also provides an example of a pre-treatment method, which
would facilitate the subsequent recovery of other precious
metal [51].
Mass Balance and Possibility of Reuse of Iron
In this work 75.8% of the copper available in the PCBs has
been recovered as copper foil using bioleaching and elec-
trowinning techniques. The mass balance of iron, high-
lights that the large amounts of iron salt that is fed to the 9 k
medium, precipitates in form of jarosite. By preventing and
reducing the jarosite formation, iron would be present in the
ferrous form in the remaining solution after electrowinning,
with the possibility to be recycled for further bioleaching
activity of the bacteria. However, in this work only 4.4 wt%
of iron remained in the solution after electrowinning. To
prevent this loss in future experiments the following options
are suggested:
1. The addition of sulphur to the medium; as the bacteria is
both sulphur and iron oxidiser, it is expected that sulphur
would be converted to sulphuric acid, therefore lowering
the pH of medium and reducing jarosite formation.
2. The use of different growth medium; the acidophilic
basal salts and trace element mixture is a promising
medium that has been suggested by other researchers,
which contains lower amounts of ferrous sulphate and
therefore is expected to result in less jarosite formation
[52].
Recommendation and Future Research
By changing the process to continuous mode, several advan-
tages can be obtained in the future of this research. Working
in continuous mode, would provide the possibility of accu-
mulation of metals in the bioleachate, and consequently in
the electrowinning tank. This would help the plating of other
base metals such as zinc and nickel, when their concentra-
tion becomes significant. Using a feed and bleed system, the
concentration of copper in the electrowinning process would
be maintained at a level where the formation of a copper foil,
with optimum physical properties, would be maintained.
After large scale application, a thorough techno-economic
assessment is necessary for evaluating the feasibility of the
process.
Applying Life Cycle Assessment, would be very helpful
for quantifying the environmental impact of the process
as it has been performed in previous research studies [9,
53]. As mentioned earlier, the iron species remains in the
13

3134
leachate in the ferrous form and can potentially be reused
for the next batches of bioleaching, as targeted in future
work.
The results obtained in this work provide pure cop-
per foil as a value-added product for return to the market
from discarded IT networking and telecommunication
equipment.
Conclusion
In this study, the closed-loop process of copper recovery
from PCBs was investigated. By combining bioleaching and
electrowinning, a model of closed-loop recycling of metals
from PCBs was demonstrated, which selectively extracted
and recovered copper. This includes the solubilisation of
copper from PCBs using an environmentally friendly
method of bioleaching, and copper foil production through
electrowinning. In this single batch method, 75.8% of copper
available in PCB was recovered as pure copper foil, suit-
able for multiple applications including the manufacturing
of PCBs. In the present study, the use of the 9 k medium
requires a large fraction of ferrous sulphate for bacterial
growth, which resulted in the excessive byproduct formation
in the form of jarosite. It is expected that the careful reduc-
tion of jarosite formation, which could be achieved by modi-
fying the growth medium, would provide a source or iron
for the next bioleaching batches, while reducing potential
contamination in electrowinning. In addition, this approach
of selective copper separation from WEEE provides a pre-
treatment method, which can facilitate and promote the sub-
sequent recovery of other precious metals, which otherwise
might be hindered by the presence of copper. Bioleaching
has been demonstrated for the solubilisation of a large num-
ber of metals, and it is expected that selective electrowinning
from leachate can be defined for other metals. Therefore,
this model should be targeted as a general method of closed-
loop recycling for metals from WEEE and other solid wastes
containing metals, to support a circular economy with high
value for several industrial applications.
Acknowledgment  The authors would like to thank Prof. David Barrie
Johnson for providing the A. ferrooxidans bacteria; and Innovate UK
and Network 2 Supplies Limited for funding. We would additionally
like to thank Network 2 Supplies Limited for providing the waste PCBs
used throughout this study.
Compliance with Ethical Standards  Valoriz. 1, 107–120 (2010)
Competing interest  The authors declare the following financial inter-
ests/personal relationships, which may be considered as potential com-
peting interests: this work is part of an Innovate UK funded Knowledge
Transfer Partnership between Coventry University and Network 2 Sup-
plies Limited.
13
Waste and Biomass Valorization (2021) 12:3125–3136
Open Access  This article is licensed under a Creative Commons Attri-
bution 4.0 International License, which permits use, sharing, adapta-
tion, distribution and reproduction in any medium or format, as long
as you give appropriate credit to the original author(s) and the source,
provide a link to the Creative Commons licence, and indicate if changes
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permitted by statutory regulation or exceeds the permitted use, you will
need to obtain permission directly from the copyright holder. To view a
copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
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Affiliations

Mahsa Baniasadi1,2,5 · John E. Graves1,3 · Daniel A. Ray1,2,5 · Angélique Lindamulage De Silva4 · Derek Renshaw1,2 ·

Sebastien Farnaud1,2 

1 4
Bioleaching Group, Coventry University, Priory Street, École Nationale Supérieure de Chimie de Rennes, 11 allée de
Coventry CV1 5FB, UK Beaulieu ‑ CS 50837, 35708 Rennes Cedex 7, France
2 5
Centre of Sport, Exercise and Life Sciences, Faculty Network 2 Supplies (N2S) Ltd, Network House, Western
of Health and Life Sciences, Coventry University, Priory Way, Bury St Edmunds, Bury Saint Edmunds IP33 3SP, UK
Street, Coventry CV1 5FB, UK
3
Functional Materials Group, IFTC, Faculty of Engineering,
Environment and Computing, Coventry University, Priory
Street, Coventry CV1 5FB, UK

13